New products obtainable from resins



I condensation hydrating agent such as zinc chloride (for excalculatedon the resinous aigo I Patented Oct. 20, 1931 rRonUoTs oBTAI nB'Il rnoi/L meme; i

eUs'rAv' MAmint,- or conoenrl nonwninn,

,nss enoas so GENERAL iro-niawiii ap ease). med March 2c, 1928, seriano: 263,293, and neenmnjz ivrareh 28;119'27? 1 The present inventionrelates to' new products obtainable from natural resin-aclds or phenolsand to a process of preparing same.

We have found, that when reacting with dehydrating agents, such as zincchloride,

upon natural resin-acids, such as colophony,

at temperatures ranging from aboutl to 1 611151011 wlthout limiting:itthereto, the parts 200 0. water and carbon monoxide are split oflf. Wehave further foundthat when re acting upon the same compounds and thecondensation products of resin-acids with phenols (see our copendingapplication Ser. N 0. 250,332, filed Jan. 28, 1928) with aralkylhalogenides such as benzyl chloride, Xylylchloride andchlorobenzylchlorides in the presence of small quantities of a suitabledeample, 1 to 3%; masses) at temperatures of about '100200 0., besideswater and carbon monoxide, hydrochloric acid and small quantities of agas which will burn with a luminous flame are evolved whereby probablyaralkyl residues enter the molecule of the resin-acids and the resinacid-phenol condensation products and COOH groups are split off. Thereaction is complete when the development of gaseous substances ceases.The resinous materials thus obtainable form yellow to red brown masseshaving higher melting points thanthe starting materials, soluble in mostorganic solvents, for instance alcohol, ether,

tetrachloromethane, glacial acetic acid, benzene and turpentine. The newmaterials are soluble in strong sulfuric acid generally with a browncoloration whereby in most cases sulfonation already occurs at roomtemperature. Thesulfonic acids thus obtainable may also be preparedwithout nated products by the addition of strong sulfuric acid, forinstance of about 100% strength, to the reaction mixtures attemperatures at which the same are still liquid and cooling in such amanner that the melts always remainv liquid. The isolation of thesulfonic acids may be performed by pouring the melts onto ice,separating the aqueous layers, neutralizing them and salting out. o 11some cases it may be advantageous to add products of resin-acids with.

isolating the unsulfoa; suitable organic diluent,*jwhich being-byweight: I

Ewa'm;ple ilk-10. parts ,of colophony are gradually heated with =5 partsof benzyl chlo- .rideend 0.2- partsof, zinc? chloride to 1204309 U.*Assoon-jas the. development .of hydrochloric acid ceases; the reactionis finished. After-cooling, ;a yellowish, brown resinous mass which.hojl, ether,.; jbenzene and turpentine' isfob- 'rawskis reaction, (seej.Zeitschrift fl'ir angewandte .Qhemie, 1927,, page, 1100). For sulfo-..nating 1 part of the powdered condensation product is dissolved acidofabout 100% strength and'heated in this solutionat about-30%C. As soon.as-a 'sampleis soluble inwater the melt is poured-onto ice, decanted,dis- The;sulfoniciacids thus'obtainablel 7 V 'orm o-ftheir, alkali metalsalts lightyel- V is easily solubleiinal'co- .tillIlGdq It does not'show any more; the reac- N 0 tion; known'gunderthew'name -Storch-Mo- 11n 2 parts": of sulfuric solved in hot-- .wat-'er and salted out; The

product thusobtainableforms a pale colored powder, I soluble in water,which solution is able to precipitate gelatin.

Example 2.. 10.;p .graduallyheated with ridefand 0.2 partsofizincchloride to 180 C. until},- gaseoussubstances are no longerevolved; On cooling, at l yellowish brown, brittlemass is obtaineda Iarts of colophony lare p '5 parts of xylyl chlo- Q v lfavample,lOjpartsof the product-'obtainableby heating '30 parts ioffcolophonywith 10 parts of phenol ingthepresence'oflfi parts of sulfurica-Qid-JOfYGOQ B :chloride and 0.2 parts gradually heated up to'110120'G:. u'ntil the development offgas'eous substances has near: .ly ceased;The.-,1-,eaction :productuthusj ob: --tain'able ,is 'verTjnwsiIfnil-arto K that described in -Example 1; lt mayfleasily 'be sulfonated bymeans of 2 parts of sulfuricacid'ofabout e. for about 8 hours to about70-80? JG, 3 parts of benzyl-. of Zinc chloride are].

7 4 .9 addedgl'whereby' the tempenature is slowly stirred for V 100%strength at a temperature of about ride until the development of gaseoussubceased. 'Aiter having -restaneeshas nearly moved the water formedduring the reaction a by sucking 61?;200 parts of tetrachloroethanepoured onto ice,

' p small amenntsef sulfuric acid.

upon 10 parts by Wl aremixedwith the melt by perature of 'C. Now tur'icacid *o'f=1 00% strength are gradually lowered M459 The melt is somehours at this temperature. Then i-t is from the tetraehloroethanelay-steam distillathe process claimed in claim t 5. The productsobtainable according to being in the form of their alkali metal saltslight yellow to yellow powders easily soluble; in-water.r w I Thefproduct obtainable "aecondzing ,to

2, said products the process claimed in claim 3, said product being inthe form v p-owdereas'fly-seln'blein -watch testimqnywhereof wehavehereunto set ourhands. l r

, c A ARNOLD DOSER.

f "GUSTAV MA'UTI-IE I -ALEBED'THAIlSfi.

stirring at ate'm- 5 i 150 parts of suldecanted, neutralized, freedtion, and the pale yellow solution thus ob- :tained is treated wi thesodium salt of thesulfonic acidform'ed se arates. It forms a pale yellowpowder, easily soluble inwater, which solution is stable towards sodiumsulfate,

7We claim 1. The process with an aralkylhalogenide upon a condensm hsodium chloride until alkalies and which-comprises reacting 7 tionproduct of .a natural resin-acid with a Y phenolin the-:presence ofasmall amount of i suitable dehydrating agent at temperatures rangingfrom "about 100t0 200C sulfonatingthecondensationproduct and saltingout.

2. The processwhieh comprises reacting with an aralkylhalogenide upon'aconde'nsation productof colophony with a phenol in the presence otabout1 to'8'% sulfonating the condensation product and salting out. i v V 3.The process which comprises reacting tainable by treating colophony withphenol with 3 parts by Wei the presence of 02" parts by weight of zincchloride at a temperature of- 1 10'- 120 "C;, adding :to 1 part by- Weiht of "the-jcondensationzpiioduct thus ebtained two parts by "weightiQE-*S}1 lfllI"lO"'aQ1d of about 100% strength at :a temperature ofabout 70 Cl,

. of zinc chloride (calculatedii'pon the' res'inous mass) at'tem-.peratures ranging from about100 to' 200 "(1.,

ht of benzylchloride in of its sodium saltayellqw.

ht ofthe product obgradually lowering the temperature to "roomtemperature and isolating theisultfo'nic acid I formed' b'y saltingout.

"4.1 The products obtainable acoprding to theprocess claimed in claim 1,said products being in the :form of their alkali metal salts lightyellowto yellow powders easily solu- Mean-water; V i V R

